Cellulose modification with solution comprising a methylolated carbamate and a methylolated triazone



United States Patent CELLULOSE MODIFICATION WITH SOLUTION COMPRISING AMETHYLOLATED CARBAMATE AND A METHYLOLATED TRIAZONE William B. Canter,Danville, Va., and Roger N. Suiter,

Syracuse, N.Y., assignors to Dan River Mills, Incorporated, Danville,Va., a corporation of Virginia No Drawing. Filed June 9, 1964, Ser. No.373,831

12 Claims. (Cl. 8-116.3)

This invention relates to novel crease-proofing compositions and methodsfor crease-proofing cellulosic fabrics therewith.

Alkyl N,N-di-methylolcarbamates, such-as methyl and ethylN,N-dimethylolcarbamates, have been heretofore employed for the purposeof crease-proofing cellulosic fabrics. In addition, condensates offormaldehyde and triazones having the formula:

wherein R is alkyl or hydroxyalkyl having 1 to 4 carbon atoms have alsobeen employed for crease-proofing cellulosic textiles. The abovetriazone condensates may contain from 0 to 1.0 mole parts of ureaformaldehyde condensate based on the combined urea in said ureaformaldehyde condensate per mole part of triazone formaldehydecondensate and still be operable in the present invention as will beapparent in the examples.

The above-mentioned carbamates have been limited in their application inthat, in order to avoid undue damage due to chlorine retention, it isnecessary to employ acid catalysts such as zinc nitrate. The use of suchacid catalysts with the c-arbamates causes damage to various sensitivedyes such as Blue BF (Vat Blue 6-, Color Index #693325), therebylimiting the use of such carbamates to undyed fabrics or fabricscarrying dyes which are not affected.

The use of formaldehyde-triazone condensates such as those mentionedabove to produce crease-resistance has been found to give rise toundesirable odors. In addition, while the crease-resistance of thefabrics treated with formaldehyde-triazone condensates as well as thecarbamates is adequate for many purposes, there is still room forimprovement. Similarly, the tear and tensile strengths of fabricstreated with carbamates alone could stand improvement. There is alsoroom for improvement in lessening the degree of damage due to chlorineretention in the use of formaldehyde-triazone condensates forcrease-proofing and in improving the appearance ratings of such fabrics.

The present invention is based on the discovery that carbamates of thetype described above can be employed with strong acid catalysts such aszinc nitrate to impart crease-resistance to cellulosic fabrics dyed withsuch sensitive dyes as Blue BF when used in admixture with aformaldehyde-triazone condensate of the type described above. It hasalso been found that such mixtures of a formaldehyde-triazone condensateand carbamate considerably reduce the odor which ordinarily would beproduced by employment of the formaldehyde-triazone condensate alone.Still in addition, it has been found that such mixtures provide improvedcrease-resistance over that produced by the carbamates orformaldehyde-triazone ice condensates each employed alone ascrease-proofing chemicals. In addition, it has been discovered that suchmixtures, when applied to cellulosic fabrics and cured thereon, providemuch less damage due to retained chlorine than in the case offormaldehyde-triazone condensates employed alOne and much improvedappearance ratings over the case where formaldehyde-triazlonecondensates alone are employed. It has been further discovered that themixtures, when applied to cellulosic textiles and cured thereon, resultin considerably improved tear and tensile strengths in the textile ascompared with textiles treated with carbamates alone.

The relative amounts of formaldehyde-triazone condensates and carbamatesemployed in the novel mixtures of the present invention can vary widelyand preferably range from 0.05 to 1.5 weight parts of theformaldehydetriaz-one condensate per weight part of the carbamate. Themixtures are advantageously employed in aqueous solution. The solidscontent of total crease-proofing chemical, i.e., carbamate andformaldehyde-triazone condensate, in the aqueous treating solution canvary over a wide range and preferably would not extend below 2 per centnor above percent. The aqueous treating solution can also contain otheringredients such as softeners, wetting agents and the like in additionto a suitable curing catalyst such as zinc nitrate, magnesium chloride,isopropanolamine hydrochloride, or mixtures thereof, and the like.

The aqueous treating solutions are applied to the cellulosic fabric andconventional techniques such as padding can be employed. The pick-up onthe fabric can also vary over a wide range, e.g., wet pick-ups of 50 topercent based on the weight of the fabric.

After application to the fabric the crease-proofing chemicals thuscarried by the fabric are cured under suitable curing conditions such asat a curing temperature of 250 to 360 F. for 5 minutes to 1 minute. Ifdesired, the fabric can be dried after application of the treatingsolution and prior to curing. While air drying at ambient temperaturescan be employed, it is preferred and more expeditious to dry at elevatedtemperatures.

The fabric to be treated may be prepared in any desired manner such asby singeing, desizing, bleaching, and other operations prior toimpregnating with the creaseproofing chemical and novel catalystaccording to the present invention. Substantially any type of cellulosicfabric can be treated according to this invention. For example, 100percent cotton woven fabrics, cottonsynthetic fiber blends, 100 percentrayon, rayon-synthetic fiber blends, rayon-cotton blends, all can betreated in accordance with this invention to provide the advantages setforth hereinabove.

The following examples are presented. Unless otherwise specified, thepercentages and parts set forth in the examples are by weight and thetemperatures set forth are in degrees Fahrenheit. The crease-resistancevalues were determined by the Monsanto Crease Recovery Test (A.A.T.C.C.Tentative Test Method 66-1959T). Reflectance values were determined on aHunter Model D-40 Reflectometer using a blue filter.

Example 1 An aqueous treating solution was prepared containing 14percent of a 57 percent solids aqueous solution of methyl N,Ndimethylolcarbamate; 2.5 percent of a catalyst solution containing 36.4percent solids of zinc nitrate and sodium hypophosphite in a weightratio of 3.72 parts zinc nitrate per part sodium hyphosphite and 0.2percent of a nonionic wetting agent and designated Composition A.

A second aqueous treating solution was prepared containing 10.5 percentof a 57 percent solids aqueous solution of methylN,N-dimethylolcarbamate; 3.5 percent of a 47.4 percent solids aqueoussolution of a N,N' dimethylol 5 hydroxyethyl tetrahydro s triazone-2 ina ratio of 60 mole percent of said triazone and 40 mole percent ofdimethylol urea and containing 5 percent excess formaldehyde; 2.5percent of the above-mentioned catalyst solution of zinc nitrate andsodium hypophosphite and 0.2 percent of a nonionic wetting agent and wasdesignated Composition B.

Compositions A and B were separately applied to 100 percent cottonfabric by padding to a 68 percent wet pick-up based on the weight offabric. The fabric in each case had been dyed with Blue BF as identifiedhereinbefore in the conventional manner. The impregnated fabric was ovendried at 300 F. for 56 seconds and then cured at 340 F. for 70 seconds.

The fabric treated with Composition A showed a severe color change fromthe desired blue to a green shade. The fabric treated with Composition Bshowed no detectable shade change. The physical properties of thefabrics so treated are given below:

Composition A Composition B Composition B contained 0.166 part of saidtriazone per part of said carbamate.

Example 2 An aqueous treating solution was prepared containing 14percent of a 57 percent solids aqueous solution of methyl N,Ndimethylolcarbamate; 2.5 percent of the catalyst solution used inExample 1 and 0.2 percent of a nonionic wetting agent and designated asComposition C.

A second aqueous treating solution was prepared containing 12.3 percentof a 57 percent solids aqueous solution of methyl N,Ndimethylolcarbamate; 1.7 percent of a 69 percent solids aqueous solutionof (a) 84 mole percent N,N dimethylol 5 ethyltetrahydro striazone-Z and(b) 16 mole percent dimethylol urea with 5 percent excess formaldehyde;2.5 percent of the catalyst solution described in Example 1 and 0.2percent of a nonionic wetting agent and was designated as Composition D.

Compositions C and D were individually applied to cotton fabric whichwas dyed with Blue BF as identified hereinbefore. The application wasperformed in the same manner as described in Example 1 and theimpregnated fabric was dried and cured in the manner set forth inExample 1. The fabric treated with Composition C underwent a severecolor change and presented a green shad rather than the original blueshade. Composition D produced little, if any, noticeable color change.Composition D contained 0.116 part of said triazone per part of saidcarbamate.

Example 3 Three yards of cotton cloth were padded through an aqueoussolution containing 130 pounds of a 43 percent solids aqueous solutionof a resin mixture of (a) 70 mole percent 011 N,N dimethylol 5hydroxyethyltetrahydro S triazone 2 and (b) 30 mole percent of dimethylolurea, 20 percent excess formaldehyde and sodium phosphate; 80pounds of a 53 percent solids aqueous solution of methyl N,Ndimethylolcarbamate containing a 35 percent excess formaldehyde; poundsof an aqueous solution containing 25 percent magnesium chloride and 25percent Zinc nitrate; 40 pounds of a 25 percent solids aqueous emulsionof polyethylene as a softener; 20 pounds of an acetic acid salt of acondensate of stearic acid and aminoethyl ethanolamine as an additionalsoftener; 20 pounds of a 10 percent aqueous solution of polyvinylalcoholand 3 pounds of a nonionic wetting agent. Approximately 70 percent ofthe treating solution based on the weight of fabric was picked up by thefabric. The treated fabric was thereafter dried at about 250 F. andcured for 70 seconds at 340 F. Thereafter, the cured fabric was washedand Sanforized. The thus treated fabric was then tested and found tohave a filling tensile strength by the Grab method of 39, a filling tearstrength by the Trapezoid method of 2.6, a crease resistance of 273 anda percent damage due to retained chlorine of 5 percent (as determined byA.A.T.C.C. Standard Test Method 92-1962) and a wash and wear appearancerating of 4 to 5 (A.A.T.C.C. Tentative Test Method 88-1960). Thetreating bath contained a total of 0.945 part of the above-identifiedtriazone per part of the above-identified carbamate.

Example 4 Three yards of cotton fabric were impregnated at 150 F. withan aqueous solution containing 9 percent of a 43 percent solids aqueoussolution of a resin mixture of (a) 70 mole percent of N,N dimethylol 5hydroxyethyltetrahydro S triazone 2 and (b) 30 mole percent ofdimethylolurea, 20 percent excess formaldehyde and sodium phosphate; 9percent of a 53 percent solids aqueous solution of methyl N,Ndimethylolcarbamate containing a 35 percent excess formaldehyde; 3.4percent of a percent solids aqueous solution of magnesium chloridehexahydrate; 3 percent of a 25 percent solids aqueous emulsion ofpolyethylene as a softener; 1.5 percent of an acetic acid salt of acondensate of stearic acid and aminoethyl ethanolamine as an additionalsoftener; 1.5 percent of a 10 percent aqueous solution ofpolyvinylalcohol and 0.3 percent of a nonionic wetting agent. Thetreating solution contained a total of 0.568 part of theabove-identified triazone per part of the above-identified carbamate.The fabric was dried at 250 F. and then cured at 340 F. for seconds. Itwas then washed and Sanforized.

The thus treated fabric had considerably less odor than cloth treatedwith a similar composition with the exception that the 9 percent of the53 percent solids carbamate solution was replaced by the 43 percentsolids solution of the triazone and dimethylolurea as described indetail above, thus giving a total of 18 percent of said 43 percentsolids aqeuous solution.

Example 5 Treating solution E was prepared containing 18 percent of a 53percent solids aqueous solution of methyl N,N dimethylolcarbamatecontaining a 35 percent excess formaldehyde; 3 percent of a 40 percentsolids aqueous emulsion of polyethylene as a softener; 3.25 percent ofan aqueous solution containing 25 percent magnesium chloride hexahydrateand 15 percent of isopropanolarnine hydrochloride; and 0.2 percent of anonionic wetting agent. Composition F was prepared from the sameingredients except that instead of 18 percent of the 53 percent solidssolution of carbamate as described above, 14 percent was employed, and,in addition, 5 percent of a 43 percent solids aqueous solution of aresin mixture of (a) 70 mole percent ofN,N-dimethylol-S-hydroxyethyltetra hydro-S-triazone-Z and (b) 30 molepercent of dimethylolurea, 20 percent excess formaldehyde and sodiumphosphate was included.

Compositions E and F were applied to cotton fabric to a wet pick-up ofabout 70 percent, the fabric then was Example 1. The fabric treated inComposition E underwent a severe color change and presented a greenshade rather than the original blue shade. Composition H producedlittle, if any, noticeable color change. Composition Composition EComposition F Orig. 1 cw 5 cw. cw Orig. 1 cw 5 cw. 10 cw Creaseresistance 280 Filling tensile. Filling tear 1. 4 Reflectance:

Initial 80. 5

Suter scorch 75. 3 Appearance:

Spin dry 4. 5

Tumble dry 5 Percent tensile loss C12 retained... 5

It is noted that the crease resistance, tensil and tear strengths,reflectance values and appearance ratings for the fabric treated withComposition F was at least as good as if not better than fabric treatedwith Composition E. In addition, the degree of damage due to chlorineretention for the fabric treated with Composition F was substantiallybetter than that for the fabric treated with Composition E. The creaseresistance, filling tensile and tear strengths, reflectance, wash andwear appearance ratings and damage due to retained chlorine were alldetermined by the test methods previously identified.

Composition F contained a total of 0.203 part of the above-identifiedtriazone per part of the above-identified carbamate. Similar comparativeresults are obtained by treating cotton fabric with the same solutionwherein, however, there is contained 0.258 part of the above-identifiedtriazone per part of the above-identified carbamate. In addition,similar results were obtained from compositions similar to that ofComposition F wherein, however, there was contained 0.756 part of theabove-identified triazone per part of the above-identified carbamate.

Similar comparative results are obtained when, in place of the 43percent solids solution identified above, there is substituted a 47.4percent aqueous solution of a resin mixture containing (a) approximately60 mole percent of N,N dimethylol-S-hydroxyethyltetrahydro-S-triazone-Zand (b) 40 mole percent of dimethylolurea and 5 percent excessformaldehyde wherein, for example, there is present 0.563 part of saidtriazone per part of the aboveidentified carbamate.

The foregoing description is intended for purposes of illustration onlyand not as a limitation on the scope of this invention inasmuch asobvious equivalents and modifications will be apparent to those skilledin the art without departing from the scope of the invention.

Example 6 An aqueous treating solution was prepared containing 14percent of a 57 percent solids aqueous solution of methylN,N-dimethylolcarbamate; 2.5 percent of the catalyst solution used inExample 1 and 0.2 percent of a nonionic wetting agent and designated asComposition G.

A second aqueous treating solution was prepared containing 11.9 percentof a 57 percent solids aqueous solution of methylN,N-dimethylolcarbamat-e; 2.1 percent of a 69 percent solids aqueoussolution of N,N-dimethylol- H contained 0.214 part of said triazone perpart of said carbamate.

What is claimed is:

1. Novel composition for treating cellulosic fabrics comprising anaqueous solution containing an alkyl N,N- dimethylol-carbamate whereinsaid alkyl group contains 1 to 4 carbon atoms and 0.05 to 1.5 weightparts of a condensate of formaldehyde and a triazone of the formula:

wherein R is selected from the class consisting of alkyl or hydroxyalkylhaving 1 to 4 carbon atoms per weight part of said alkylN,N-dimethylolcarbamate.

2. Composition as claimed in claim 1 wherein said alkylN,N-dimethylolcarbamate is methyl N,N-dimethylolcarbamate.

3. Composition as claimed in claim 2 wherein said condensate isN,N-dimethylol 5 ethyl-tetrahydro-s-trialone-2.

4. Composition as claimed in claim 2 wherein said condensate isN,N'-dimethylol-5-hydroxyethyl-tetrahydro-striazone-2.

5. Composition as claimed in claim 3 wherein said composition alsocontains N,N'-dimethylol urea.

6. Composition as claimed in claim 4 wherein said composition alsocontains N,N'-dimethylolurea.

7. Method of treating cellulosic fabric comprising the steps of applyingto said fabric an aqueous solution containing crease-proofing chemicalscomprising an alkyl N,N-dimethylolcarbamate wherein said alkyl groupcontains l to 4 carbon atoms and 0.05 to 1.5 weight parts of acondensate of formaldehyde and a triazone of the formula:

wherein R is selected from the class consisting of alkyl or hydroxyalkylhaving 1 to 4 carbon atoms per weight part of saidN,N-dimethylolcarbamate; and thereafter heating said fabric to dry andcure said crease-proofing chemicals.

8. Method as claimed in claim 7 wherein said alkylN,N-dimethylolcarbamate is methyl N,N-dimethylolcarbamate.

:8 9. Method as claimed in claim 8 wherein said con- 12. Composition asclaimed in claim 10 wherein said densate is- N,N dimethylol 5 ethyltetrahydro scomposition also contains N,N-dimethylol urea.

triaz0ne-2.

10. Method as claimed in claim 8 wherein said con- No references cited.dcnsate is N,N'-dimethyl0l-5-hydroxyethyl-tetrahydro-s- 5 triaZone 2NORMAN G. TORCHIN, Primary Examiner.

11. Method as claimed in claim 9 wherein saidcomposi- CANNON, AssistantExaminer tion also contains N,N-dimethyl0l urea.

1. NOVEL COMPOSITION FOR TREATING CELLULOSIC FABRICS COMPRISING ANAQUEOUS SOLUTION CONTAINING AN ALKYL N,NDIMETHYLOL-CARBAMATE WHEREINSAID ALKYL GROUP CONTAINS 1 TO 4 CARBON ATOMS AND 0.05 TO 1.5 WEIGHTPARTS OF A CONDENSATE OF FORMALDEHYDE AND A TRIAZONE OF THE FORMULA: 7.METHOD OF TREATING CELLULOSIC FABRIC COMPRISING THE STEPS OF APPLYING TOSAID FABRIC AN AQUEOUS SOLUTION CONTAINING CREASE-PROOFING CHEMICALSCOMPRISING AN ALKYL N,N-DIMETHYLOLCARBAMATE WHEREIN SAID ALKYL GROUPCONTAINS 1 TO 4 CARBON ATOMS AND 0.05 TO 1.5 WEIGHT PARTS OF ACONDENSATE OF FORMALDEHYDE AND A TRIAZONE OF THE FORMULA: